TWI861285B - Composition, hardened body, sealing material for organic electroluminescent display element, and organic electroluminescence display device - Google Patents

Abstract

A composition containing a monomer component which contains a fluorine-containing monomer having a fluorine atom and a carbon-carbon unsaturated double bond, and a photopolymerization initiator, wherein at least a portion of the monomer component is a high-viscosity monomer with a viscosity measured by an E-type viscometer at 25°C of 50 mPa·s or higher, and the viscosity of the composition measured by an E-type viscometer at 25°C is at least 3 mPa·s but not more than 50 mPa·s.

Description

Composition, hardened body, sealing material for organic electroluminescent display element, and organic electroluminescent display device

The present invention relates to a composition and a cured product thereof. In addition, the present invention relates to a sealing material for an organic electroluminescent (EL) display element and an organic EL display device containing the sealing material.

Organic electroluminescent display elements (also called organic EL display elements, organic EL elements, or OLED elements) have attracted attention as elements that can emit light at high brightness. However, organic EL display elements have the problem of degradation of light emission characteristics due to moisture.

In order to solve such a problem, some people have studied the technology of using a sealing material formed by stacking organic films and inorganic films to seal the organic EL display element and prevent degradation caused by moisture (for example, patent documents 1-2). [Prior technical documents] [Patent document]

[Patent document 1] Japanese Patent Publication No. 2001-307873 [Patent document 2] Japanese Patent Publication No. 2009-37812

[The problem that the invention wants to solve]

In recent years, the requirements for the properties of organic EL display elements have increased, and sealing materials that can achieve higher reliability and durability are required.

As for the method of forming the sealing material, there is a known method of forming an organic film by coating and curing a resin composition, and then laminating an inorganic film on the organic film. This method has the problem that when the surface of the organic film is uneven, the adhesion with the inorganic film is reduced. In addition, when the resin composition is coated by inkjet method, the coating liquid ejected from the inkjet nozzle will meander and deviate from the predetermined range, making it difficult to form a correct organic film.

Therefore, the object of the present invention is to provide a composition that can accurately form an organic film with less surface unevenness within a predetermined range. In addition, the object of the present invention is to provide a hardened body of the above composition, and the hardened body is effective as a sealing material for an organic EL display element. In addition, the object of the present invention is to provide a sealing material for an organic EL display element containing the above hardened body, and to provide an organic EL display device containing the sealing material. [Means for solving the problem]

One aspect of the present invention is a composition comprising: a monomer component containing a fluorine-containing monomer having a fluorine atom and a carbon-carbon unsaturated double bond, and a photopolymerization initiator. At least a portion of the monomer component is a high viscosity monomer having a viscosity of 50 mPa·s or more measured at 25°C using an E-type viscometer. Furthermore, the viscosity of the composition measured at 25°C using an E-type viscometer is 3 mPa·s or more and 50 mPa·s or less.

Since the above composition has excellent surface flatness and straightness, an organic film with less surface irregularities can be accurately formed within a predetermined range.

In the composition claimed in one embodiment, 5-65 mass % of the above-mentioned monomer component may be the above-mentioned high-viscosity monomer.

In one embodiment, at least a portion of the above-mentioned monomer components may be a multifunctional monomer having two or more carbon-carbon unsaturated double bonds.

In the composition claimed in one embodiment, 70-98 mass % of the above-mentioned monomer component may be the above-mentioned multifunctional monomer.

In one embodiment, at least a portion of the high viscosity monomers may be monofunctional monomers having one carbon-carbon unsaturated double bond.

In the composition claimed in one embodiment, 10-60 mass % of the high viscosity monomer may be the monofunctional monomer.

The above composition can be preferably used as a sealant for an organic electroluminescent display element.

Another aspect of the present invention relates to a hardened body, which is formed by hardening the above composition.

Still another aspect of the present invention relates to a sealing material for an organic electroluminescent display element, comprising the above-mentioned hardened body.

Yet another aspect of the present invention relates to a sealing material for an organic electroluminescent display element, comprising a laminated body formed by laminating an inorganic film and an organic film, wherein the organic film comprises a hardened body as described in claim 8.

Another aspect of the present invention relates to an organic electroluminescent display device, comprising an organic electroluminescent display element and a sealing material for the organic electroluminescent display element. [Effect of the invention]

According to the present invention, a composition is provided that can accurately form an organic film with less surface irregularities within a predetermined range. According to the present invention, a hardened body of the composition is provided, and the hardened body is effective as a sealing material for an organic EL display element. In addition, according to the present invention, a sealing material for an organic EL display element containing the hardened body is provided, and an organic EL display device containing the sealing material is provided.

The following describes in detail the preferred embodiments of the present invention.

<Composition> The composition of this embodiment contains: a monomer component including a fluorine-containing monomer, and a photopolymerization initiator. In this embodiment, at least a portion of the monomer component is a high-viscosity monomer having a viscosity of 50 mPa･s or more measured at 25°C using an E-type viscometer. In addition, the viscosity of the composition of this embodiment measured at 25°C using an E-type viscometer is 3 mPa･s or more and 50 mPa･s or less.

Since the composition of this embodiment has a viscosity within the above range, it can be ideally used in the inkjet method. Since the surface flatness and straightness are excellent, an organic film with less surface unevenness can be accurately formed within a predetermined range.

The reasons for achieving the above effects are considered to be as follows, but are not limited thereto. First, it is considered that the composition of the present embodiment contains a fluorine-containing monomer, so the surface free energy becomes low, and after coating, the coating surface is easily flattened, and an organic film with less surface unevenness can be formed. In addition, the composition of the present embodiment contains a high-viscosity monomer, and is less likely to meander when ejected from an inkjet nozzle (i.e., the straightness is improved), and an accurate organic film can be formed in a predetermined range.

At least a portion of the monomer components of this embodiment is a high viscosity monomer having a viscosity of 50 mPa·s or more measured at 25°C using an E-type viscometer. The viscosity of the high viscosity monomer is preferably 100 mPa·s or more, more preferably 150 mPa·s or more. Furthermore, the viscosity of the high viscosity monomer is preferably 1000 mPa·s or less, more preferably 500 mPa·s or less, and even more preferably 300 mPa·s or less. That is, the viscosity of the high viscosity monomer, as measured by an E-type viscometer at 25°C, may be, for example, 50-1000mPa･s, 50-500mPa･s, 50-300mPa･s, 100-1000mPa･s, 100-500mPa･s, 100-300mPa･s, 150-1000mPa･s, 150-500mPa･s or 150-300mPa･s.

The viscosity of the composition of the present embodiment (viscosity measured at 25°C using an E-type viscometer) is 3 mPa･s or more, preferably 5 mPa･s or more, and more preferably 10 mPa･s or more. In addition, the viscosity of the composition of the present embodiment (viscosity measured at 25°C using an E-type viscometer) is 50 mPa･s or less, preferably 45 mPa･s or less, and more preferably 40 mPa･s or less. If it is within such a viscosity range, there is a tendency to further improve the surface flatness. That is, the viscosity of the composition of the present embodiment, measured at 25° C. using an E-type viscometer, may be, for example, 3 to 50 mPa･s, 3 to 45 mPa･s, 3 to 40 mPa･s, 5 to 50 mPa･s, 5 to 45 mPa･s, 5 to 40 mPa･s, 10 to 50 mPa･s, 10 to 45 mPa･s, or 10 to 40 mPa･s.

The composition of this embodiment may contain a high viscosity monomer and a low viscosity monomer (a monomer having a viscosity of less than 50 mPa·s measured at 25°C using an E-type viscometer) as monomer components. The ratio of the high viscosity monomer to the low viscosity monomer may be appropriately changed within the range of the viscosity of the composition within the above numerical range.

The proportion of the high-viscosity monomer in the monomer component may be, for example, 5% by mass or more, preferably 7% by mass or more, and more preferably 9% by mass or more. By increasing the proportion of the high-viscosity monomer, there is a tendency to further improve the straightness. In addition, the proportion of the high-viscosity monomer in the monomer component may be, for example, 65% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less. By reducing the proportion of the high-viscosity monomer, there is a tendency to reduce the viscosity of the composition and further improve the sprayability. That is, the proportion of the high viscosity monomer in the monomer component may be, for example, 5-65 mass%, 5-60 mass%, 5-55 mass%, 5-50 mass%, 5-45 mass%, 5-40 mass%, 5-35 mass%, 7-65 mass%, 7-60 mass%, 7-55 mass%, 7-50 mass%, 7-45 mass%, 7-40 mass%, 7-35 mass%, 9-65 mass%, 9-60 mass%, 9-55 mass%, 9-50 mass%, 9-45 mass%, 9-40 mass%, or 9-35 mass%.

The composition of this embodiment may contain a monofunctional monomer having one carbon-carbon unsaturated double bond and a polyfunctional monomer having two or more carbon-carbon unsaturated double bonds as monomer components.

The proportion of the multifunctional monomer in the monomer component may be, for example, 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more. By increasing the proportion of the multifunctional monomer, the moisture permeability of the hardened body is improved, and the straightness is further improved. In addition, the proportion of the multifunctional monomer in the monomer component may be, for example, 98% by mass or less, preferably 97% by mass or less, and more preferably 96% by mass or less. By reducing the proportion of the multifunctional monomer, the surface flatness is further improved. That is, the ratio of the multifunctional monomer in the monomer component may be, for example, 70-98 mass%, 70-97 mass%, 70-96 mass%, 75-98 mass%, 75-97 mass%, 75-96 mass%, 80-98 mass%, 80-97 mass% or 80-96 mass%.

The multifunctional monomer is preferably a monomer having 2 to 6 carbon-carbon unsaturated double bonds, more preferably a monomer having 2 or 3 carbon-carbon unsaturated double bonds, and even more preferably a bifunctional monomer having 2 carbon-carbon unsaturated double bonds.

The composition of the present embodiment may contain the multifunctional monomer in the form of a high-viscosity monomer, may contain the multifunctional monomer in the form of a low-viscosity monomer, or may contain both a multifunctional monomer that is a high-viscosity monomer and a multifunctional monomer that is a low-viscosity monomer.

The composition of the present embodiment may contain the monofunctional monomer in the form of a high-viscosity monomer, may contain the monofunctional monomer in the form of a low-viscosity monomer, or may contain both a monofunctional monomer that is a high-viscosity monomer and a monofunctional monomer that is a low-viscosity monomer.

In this embodiment, at least a part of the high viscosity monomer is preferably a monofunctional monomer.

The ratio of the monofunctional monomer in the high viscosity monomer may be, for example, 9% by mass or more, preferably 10% by mass or more, more preferably 11% by mass or more, and even more preferably 12% by mass or more. Furthermore, the ratio of the monofunctional monomer in the high viscosity monomer may be, for example, 60% by mass or less, preferably 55% by mass or less, and even more preferably 50% by mass or less. By using a large amount of the monofunctional monomer in the form of a high viscosity monomer, the moisture permeability, softness, and flexibility of the cured product tend to be further improved. That is, the ratio of the monofunctional monomer in the high viscosity monomer may be, for example, 9-60 mass%, 9-55 mass%, 9-50 mass%, 10-60 mass%, 10-55 mass%, 10-50 mass%, 11-60 mass%, 11-55 mass%, 11-50 mass%, 12-60 mass%, 12-55 mass% or 12-50 mass%.

<Fluorine-containing monomer> Fluorine-containing monomers are monomers having fluorine atoms and carbon-carbon unsaturated double bonds. Fluorine-containing monomers may be used alone or in combination of two or more.

The fluorinated monomer may also be included in the monomer component in the form of a low-viscosity monomer. The viscosity of the fluorinated monomer (viscosity measured at 25°C using an E-type viscometer) may be, for example, less than 50 mPa･s, preferably less than 45 mPa･s, more preferably less than 40 mPa･s, and even more preferably less than 35 mPa･s. Furthermore, the viscosity of the fluorinated monomer (viscosity measured at 25°C using an E-type viscometer) may be, for example, greater than 1 mPa･s, greater than 2 mPa･s, or greater than 3 mPa･s. That is, the viscosity of the fluorinated monomer, as measured by an E-type viscometer at 25°C, may be, for example, 1 mPa･s or more and less than 50 mPa･s, 1 to 45 mPa･s, 1 to 40 mPa･s, 1 to 35 mPa･s, 2 mPa･s or more and less than 50 mPa･s, 2 to 45 mPa･s, 2 to 40 mPa･s, 2 to 35 mPa･s, 3 mPa･s or more and less than 50 mPa･s, 3 to 45 mPa･s, 3 to 40 mPa･s, or 3 to 35 mPa･s.

The number of fluorine atoms possessed by the fluorine-containing monomer may be 1 or more, for example, 2 or more, preferably 3 or more. In addition, the upper limit of the number of fluorine atoms possessed by the fluorine-containing monomer is not particularly limited. The number of fluorine atoms possessed by the fluorine-containing monomer may be, for example, 40 or less, preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less. That is, the number of fluorine atoms possessed by the fluorine-containing monomer may be, for example, 1 to 40, 1 to 35, 1 to 30, 1 to 25, 2 to 40, 2 to 35, 2 to 30, 2 to 25, 3 to 40, 3 to 35, 3 to 30 or 3 to 25.

The content of fluorine atoms relative to the total amount of the fluorine-containing monomer may be, for example, 1% by mass or more, preferably 2% by mass or more, and more preferably 5% by mass or more. Furthermore, the content of fluorine atoms, based on the total amount of the fluorine-containing monomer, may be, for example, 90% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less. That is, the content of fluorine atoms, based on the total amount of the fluorine-containing monomer, may be: 1-90% by mass, 1-75% by mass, 1-70% by mass, 1-65% by mass, 2-90% by mass, 2-75% by mass, 2-70% by mass, 2-65% by mass, 5-90% by mass, 5-75% by mass, 5-70% by mass, or 5-65% by mass.

The number of carbon-carbon unsaturated double bonds possessed by the fluorine-containing monomer may be 1 or more. The number of carbon-carbon unsaturated double bonds possessed by the fluorine-containing monomer may be 4 or less, but from the viewpoint of easily obtaining a hardened body with excellent flexibility, it is preferably 3 or less, and more preferably 2 or less. That is, the number of carbon-carbon unsaturated double bonds possessed by the fluorine-containing monomer may be 1 to 4, 1 to 3, or 1 to 2, for example.

The fluorine-containing monomer preferably has a (meth)acryl group as a group having a carbon-carbon double bond. That is, the fluorine-containing monomer is preferably a monomer having a fluorine atom and a (meth)acryl group. In addition, the (meth)acryl group represents an acryl group or a methacryl group.

One specific example of the fluorine-containing monomer is a compound represented by the following formula (A-1).

[Chemistry 1]

In formula (A-1), ^R1 represents a hydrogen atom or a methyl group. Also, ^R2 represents a fluorinated alkyl group or a group in which an oxygen atom is inserted into a part of the carbon-carbon bond and carbon-hydrogen bond of the fluorinated alkyl group.

A fluorinated alkyl group may be a group in which a part or all of the hydrogen atoms of an alkyl group are replaced by fluorine atoms. The number of carbon atoms of the fluorinated alkyl group is not particularly limited, and may be, for example, 1 or more, preferably 2 or more, and more preferably 3 or more. In addition, the number of carbon atoms of the fluorinated alkyl group may be, for example, 25 or less, or 20 or less. That is, the number of carbon atoms of the fluorinated alkyl group may be, for example, 1 to 25, 1 to 20, 2 to 25, 2 to 20, 3 to 25, or 3 to 20.

As the fluorinated alkyl group, a group containing a difluoromethylene group (-CF ₂ -) can be preferably used.

Specific examples of the fluorinated alkyl group include difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 1,1,1-trifluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1,1,1,2,2-pentafluoropropyl, 1,1,2,2,3,3-hexafluoropropyl, perfluoropropyl, perfluoroethylmethyl, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl, 2,2,3,3-tetrafluoropropyl, perfluoropropyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,1,2,2,3,3-heptafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, perfluorobutyl, 1,1-Bis(trifluoro)methyl-2,2,2-trifluoroethyl, 2-(perfluoropropyl)ethyl, 1,1,2,2,3,3,4,4-octafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, perfluoropentyl, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl, 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 1,1,1,2,2,3,3,4,4-nonafluoropentyl, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl, perfluorohexyl, perfluoropentylmethyl and perfluorohexyl, etc.

The group in which an oxygen atom is inserted into a part of the carbon-carbon bond and carbon-hydrogen bond in the fluorinated alkyl group (hereinafter also referred to as an oxygen-containing group of R ² ) may be a group in which the oxygen atom is inserted into a single position or may be a group in which the oxygen atom is inserted into two or more positions.

In addition, if an oxygen atom is inserted into a carbon-carbon bond, an ether bond is formed. Also, if an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, the oxygen-containing group of ^R2 can also be said to contain at least one group selected from the group consisting of an ether bond and a hydroxyl group.

Specific examples of the oxygen-containing group of R ² include groups represented by the following formulae.

[Chemistry 2]

The fluorine atom content in the compound represented by formula (A-1) may be, for example, 2% by mass or more, preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 30% by mass or more. Furthermore, the fluorine atom content in the compound represented by formula (A-1) may be, for example, 75% by mass or less, preferably 70% by mass or less, and more preferably 65% by mass or less. That is, the fluorine atom content in the compound represented by formula (A-1) may be, for example, 2-75% by mass, 2-70% by mass, 2-65% by mass, 5-75% by mass, 5-70% by mass, 5-65% by mass, 15-75% by mass, 15-70% by mass, 15-65% by mass, 30-75% by mass, 30-70% by mass, or 30-65% by mass.

One specific example of the compound represented by formula (A-1) is a compound represented by formula (A-1-1).

[Chemistry 3]

In formula (A-1-1), R ¹ represents a hydrogen atom or a methyl group, R ²¹ represents a hydrogen atom or a fluorine atom, and n represents an integer greater than 1. A plurality of R ^21s may be the same or different from each other. However, at least one of R ^21s is a fluorine atom.

n may be 1 or more, and preferably 2 or more. The upper limit of n is not particularly limited. n may be, for example, 25 or less, or 20 or less. That is, n may be, for example, 1 to 25, 1 to 20, 2 to 25, or 2 to 20.

There are plural R ^21's in formula (A-1-1), but at least one of them is a fluorine atom. Moreover, among R ^21's , preferably 2 or more are fluorine atoms, and more preferably 3 or more are fluorine atoms. All R ^21's may be fluorine atoms.

The ratio of the number of fluorine atoms to the total number of R ²¹ may be, for example, 4% or more, preferably 8% or more, and more preferably 12% or more. The ratio may be, for example, 100% or less, preferably 80% or less, and more preferably 75% or less. That is, the ratio of the number of fluorine atoms to the total number of R ²¹ may be, for example, 4-100%, 4-80%, 4-75%, 8-100%, 8-80%, 8-75%, 12-100%, 12-80%, or 12-75%.

In the compound represented by the formula (A-1-1), at least one of the divalent groups (—C(R ²¹ ) ₂ —) in the parentheses labeled with n is preferably a difluoromethylene group (—CF ₂ —).

Another specific example of the fluorine-containing monomer is a compound represented by formula (A-2).

[Chemistry 4]

In formula (A-2), R ³ represents a hydrogen atom or a methyl group. Also, R ⁴ represents a fluorinated alkanediyl group or a group in which an oxygen atom is inserted into a portion of a carbon-carbon bond or a carbon-hydrogen bond in a fluorinated alkanediyl group. A plurality of R ³ groups may be the same or different from each other.

The fluorinated alkanediyl group may be a group in which a part or all of the hydrogen atoms possessed by the alkanediyl group are replaced by fluorine atoms. The number of carbon atoms of the fluorinated alkanediyl group is not particularly limited, and may be, for example, 1 or more, preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. In addition, the number of carbon atoms of the fluorinated alkanediyl group may be, for example, 20 or less, preferably 17 or less, more preferably 15 or less, even more preferably 12 or less, and even more preferably 10 or less. That is, the number of carbon atoms of the fluorinated alkanediyl group may be, for example, 1 to 20, 1 to 17, 1 to 15, 1 to 12, 1 to 10, 2 to 20, 2 to 17, 2 to 15, 2 to 12, 2 to 10, 3 to 20, 3 to 17, 3 to 15, 3 to 12, 3 to 10, 4 to 20, 4 to 17, 4 to 15, 4 to 12, or 4 to 10.

As the fluorinated alkanediyl group, a group containing a difluoromethylene group (-CF ₂ -) can be preferably used.

Specific examples of the fluorinated alkanediyl group include a linear or branched fluorinated alkanediyl group having 1 to 17 carbon atoms (e.g., 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexafluoro-1,10-decanediyl group), a fluorinated cycloalkanediyl group having 1 to 17 carbon atoms, and the like.

The group in which an oxygen atom is inserted into a part of the carbon-carbon bond and carbon-hydrogen bond in the fluorinated alkanediyl group (hereinafter also referred to as an oxygen-containing group of R ⁴ ) may be a group in which the oxygen atom is inserted into a single position or may be a group in which the oxygen atom is inserted into two or more positions.

In addition, if an oxygen atom is inserted into a carbon-carbon bond, an ether bond is formed. Also, if an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, the oxygen-containing group of ^R4 can also be said to contain at least one group selected from the group consisting of an ether bond and a hydroxyl group.

Specific examples of the oxygen-containing group of R ⁴ include groups represented by the following formulae.

[Chemistry 5]

The fluorine atom content in the compound represented by formula (A-2) may be, for example, 4% by mass or more, preferably 8% by mass or more, and more preferably 12% by mass or more. Furthermore, the fluorine atom content in the compound represented by formula (A-2) may be, for example, 90% by mass or less, preferably 75% by mass or less, and more preferably 65% by mass or less. That is, the fluorine atom content in the compound represented by formula (A-2) may be, for example, 4 to 90% by mass, 4 to 75% by mass, 4 to 65% by mass, 8 to 90% by mass, 8 to 75% by mass, 8 to 65% by mass, 12 to 90% by mass, 12 to 75% by mass, or 12 to 65% by mass.

One specific example of the compound represented by formula (A-2) is a compound represented by formula (A-2-1).

[Chemistry 6]

In formula (A-2-1), R ³ represents a hydrogen atom or a methyl group, R ⁴¹ represents a hydrogen atom or a fluorine atom, and m represents an integer greater than 1. A plurality of R ^3s may be the same or different from each other. A plurality of R ^41s may be the same or different from each other. However, at least one of R ^41s is a fluorine atom.

m may be 1 or more, preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit of m is not particularly limited. m may be, for example, 20 or less, preferably 17 or less, more preferably 15 or less, even more preferably 12 or less, and even more preferably 10 or less. That is, m may be, for example, 1 to 20, 1 to 17, 1 to 15, 1 to 12, 1 to 10, 2 to 20, 2 to 17, 2 to 15, 2 to 12, 2 to 10, 3 to 20, 3 to 17, 3 to 15, 3 to 12, 3 to 10, 4 to 20, 4 to 17, 4 to 15, 4 to 12, or 4 to 10.

There are plural R ^41's in formula (A-2-1), but at least one of them is a fluorine atom. Moreover, among R ^41's , preferably 2 or more are fluorine atoms, and more preferably 4 or more are fluorine atoms. All R ^41's may be fluorine atoms.

The ratio of the number of fluorine atoms to the total number of R ⁴¹ may be, for example, 1% or more, preferably 5% or more, and more preferably 10% or more. The ratio may be, for example, 100% or less, preferably 95% or less, and more preferably 90% or less. That is, the ratio of the number of fluorine atoms to the total number of R ⁴¹ may be, for example, 1-100%, 1-95%, 1-90%, 5-100%, 5-95%, 5-90%, 10-100%, 10-95%, or 10-90%.

In the compound represented by the formula (A-2-1), at least one of the divalent groups (—C(R ⁴¹ ) ₂ —) in the brackets marked with m is preferably a difluoromethylene group (—CF ₂ —).

Another specific example of the fluorine-containing monomer is a compound represented by formula (A-3).

[Chemistry 7]

In formula (A-3), R ⁵ represents a hydrogen atom or a methyl group. Also, R ⁶ represents a single bond, an alkanediyl group, a fluorinated alkanediyl group, or a group in which an oxygen atom is inserted into a portion of a carbon-carbon bond or a carbon-hydrogen bond in an alkanediyl group or a fluorinated alkanediyl group. Also, Ar ¹ represents a fluorinated aryl group.

In addition, "R ⁶ represents a single bond" means that Ar ¹ is directly bonded to the oxygen atom.

The fluorinated aryl group of Ar ¹ is preferably a fluorinated phenyl group. The fluorinated phenyl group may be a group in which 1 to 5 hydrogen atoms in the phenyl group are substituted with fluorine atoms. The fluorinated phenyl group may have one or more fluorine atoms, or may have five fluorine atoms.

The number of carbon atoms of the alkanediyl group of R ⁶ is not particularly limited, and may be, for example, 1 or more. Also, the number of carbon atoms of the alkanediyl group of R ⁶ may be, for example, 17 or less, preferably 15 or less, and more preferably 12 or less. That is, the number of carbon atoms of the alkanediyl group of R ⁶ may be, for example, 1-17, 1-15, or 1-12.

Specific examples of the alkanediyl group include a linear or branched alkanediyl group having 1 to 17 carbon atoms (e.g., a methylene group, an ethylene group, etc.), a cycloalkanediyl group having 1 to 17 carbon atoms, and the like.

The fluorinated alkanediyl group of R ⁶ may be a group in which a part or all of the hydrogen atoms of the above-mentioned alkanediyl group are replaced by fluorine atoms. The number of carbon atoms of the fluorinated alkanediyl group of R ⁶ is not particularly limited, and may be, for example, 1 or more. In addition, the number of carbon atoms of the fluorinated alkanediyl group of R ⁶ may be, for example, 17 or less, preferably 15 or less, and more preferably 12 or less. That is, the number of carbon atoms of the fluorinated alkanediyl group of R ⁶ may be, for example, 1 to 17, 1 to 15, or 1 to 12.

As the fluorinated alkanediyl group for R ⁶ , a group containing a difluoromethylene group (-CF ₂ -) can be preferably used.

The group in which an oxygen atom is inserted into a part of the carbon-carbon bond and carbon-hydrogen bond in the alkanediyl group or the fluorinated alkanediyl group (hereinafter also referred to as the oxygen-containing group of R ⁶ ) may be a group in which the oxygen atom is inserted into a single position or may be a group in which the oxygen atom is inserted into two or more positions.

In addition, if an oxygen atom is inserted into a carbon-carbon bond, an ether bond is formed. Also, if an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, the oxygen-containing group of R ⁶ can also be said to contain at least one group selected from the group consisting of an ether bond and a hydroxyl group.

Specific examples of the oxygen-containing group for R ⁶ include groups containing -CH ₂ CH ₂ O- and the like.

The fluorine atom content in the compound represented by formula (A-3) may be, for example, 3% by mass or more, preferably 7% by mass or more, and more preferably 15% by mass or more. Furthermore, the fluorine atom content in the compound represented by formula (A-3) may be, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less. That is, the fluorine atom content in the compound represented by formula (A-3) may be, for example, 3 to 90% by mass, 3 to 80% by mass, 3 to 70% by mass, 7 to 90% by mass, 7 to 80% by mass, 7 to 70% by mass, 15 to 90% by mass, 15 to 80% by mass, or 15 to 70% by mass.

One specific example of the compound represented by formula (A-3) is a compound represented by formula (A-3-1).

[Chemistry 8]

In formula (A-3-1), R ⁵ represents a hydrogen atom or a methyl group, R ⁶¹ represents a hydrogen atom or a fluorine atom, R ⁶² represents a hydrogen atom or a fluorine atom, and p represents an integer greater than or equal to 0. When p is greater than or equal to 1, a plurality of R ^61s may be the same or different from each other. Also, a plurality of R ^62s may be the same or different from each other. However, at least one of R ^62s is a fluorine atom.

p represents an integer greater than or equal to 0. Here, p being 0 indicates that the benzene ring and the oxygen atom are directly bonded. p may also be an integer greater than or equal to 1. In addition, there is no particular limitation on the upper limit of p. p may be, for example, less than or equal to 17, preferably less than or equal to 15, and more preferably less than or equal to 12. That is, p may be, for example, 1 to 17, 1 to 15, or 1 to 12.

When R ⁶¹ exists in formula (A-3-1) (that is, when p is an integer greater than 1), R ⁶¹ may be all hydrogen atoms, all fluorine atoms, or a part of them may be hydrogen atoms and the rest (hereinafter sometimes referred to as the other part) may be fluorine atoms.

There are multiple R ⁶² in formula (A-3-1), and at least one of them is a fluorine atom. Moreover, among R ⁶² , two or more may be fluorine atoms, or three or more may be fluorine atoms. Moreover, all (5) R ⁶² may be fluorine atoms.

The ratio of the number of fluorine atoms to the total number of R ⁶¹ and R ⁶² may be, for example, 5% or more, preferably 10% or more, and more preferably 20% or more. The ratio may be, for example, 100% or less, preferably 95% or less, and more preferably 80% or less. That is, the ratio of the number of fluorine atoms to the total number of R ⁶¹ and R ⁶² may be, for example, 5-100%, 5-95%, 5-80%, 10-100%, 10-95%, 10-80%, 20-100%, 20-95%, or 20-80%.

In a preferred embodiment, the fluorine-containing monomer preferably includes at least one selected from the group consisting of a compound represented by formula (A-1), a compound represented by formula (A-2), and a compound represented by formula (A-3).

In another desirable aspect, the fluorine-containing monomer preferably comprises at least one selected from the group consisting of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexafluoro-1,10-decanediol di(meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, and 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate.

The fluorine-containing monomers are not limited to the above-mentioned compounds.

In this embodiment, the monomer component may further contain other monomers (i.e., monomers without fluorine atoms) other than fluorine-containing monomers (hereinafter also referred to as monomer (B)). Monomer (B) may be a monomer having a carbon-carbon unsaturated double bond and having no fluorine atoms. Monomer (B) is preferably a monomer having a vinyl group as a carbon-carbon unsaturated double bond, and more preferably a monomer having a (meth)acryloyl group as a carbon-carbon unsaturated double bond.

The proportion of the fluorinated monomer in the monomer component is not particularly limited, and may be, for example, 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.008% by mass or more. Furthermore, the proportion of the fluorinated monomer in the monomer component may be, for example, 97% by mass or less, preferably 95% by mass or less, and more preferably 93% by mass or less. That is, the proportion of the fluorinated monomer in the monomer component may be, for example: 0.001-97% by mass, 0.001-95% by mass, 0.001-93% by mass, 0.005-97% by mass, 0.005-95% by mass, 0.005-93% by mass, 0.008-97% by mass, 0.008-95% by mass, or 0.008-93% by mass.

The ratio of the fluorinated monomer in the monomer component is preferably 0.01 mass % or more, more preferably 0.1 to 10 mass %, more preferably 0.3 to 7 mass %, and even more preferably 0.5 to 5 mass %, from the viewpoint of improving the surface flatness and straightness. That is, the ratio of the fluorinated monomer in the monomer component may be, for example, 0.01 to 10 mass %, 0.01 to 7 mass %, 0.01 to 5 mass %, 0.1 to 10 mass %, 0.1 to 7 mass %, 0.1 to 5 mass %, 0.3 to 10 mass %, 0.3 to 7 mass %, 0.3 to 5 mass %, 0.5 to 10 mass %, 0.5 to 7 mass %, or 0.5 to 5 mass %.

The content of fluorine atoms relative to the total amount of monomer components may be, for example, 0.005% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more. Furthermore, the content of fluorine atoms, based on the total amount of monomer components, may be, for example, 75% by mass or less, preferably 70% by mass or less, and even more preferably 65% by mass or less. That is, the content of fluorine atoms relative to the total amount of monomer components can be, for example, 0.005-75 mass%, 0.005-70 mass%, 0.005-65 mass%, 0.5-75 mass%, 0.5-70 mass%, 0.5-65 mass%, 1-75 mass%, 1-70 mass%, 1-65 mass%, 2-75 mass%, 2-70 mass%, 2-65 mass%, 5-75 mass%, 5-70 mass% or 5-65 mass%.

The monomer (B) may be a high viscosity monomer or a low viscosity monomer, but at least a portion of the monomer (B) is preferably a high viscosity monomer. The monomer component may contain two or more monomers (B), in which case all of the two or more monomers (B) may be high viscosity monomers, or one portion of the two or more monomers (B) may be a high viscosity monomer and the other portion may be a low viscosity monomer.

Among the monomers (B), the high viscosity monomers include: 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate (2-HPA), 2-(meth)acryloyloxyhexahydro-1-phenylene dicarboxylic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropylphthalic acid, EO modified phenol (meth)acrylate, EO modified cresol (meth)acrylate, EO modified nonylphenol (meth)acrylate, PO modified nonylphenol (meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate esters, trihydroxymethylpropane tri(meth)acrylate, ethoxylated trihydroxymethylpropane tri(meth)acrylate, propoxylated trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dihydroxymethylpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

Among the monomers (B), low viscosity monomers include, for example, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, cyclohexyl(meth)acrylate, isoborneol(meth)acrylate, benzyl(meth)acrylate, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isooctyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, and the like.

The monomer (B) may be a monofunctional monomer or a polyfunctional monomer, but at least a portion of the monomer (B) is preferably a monofunctional monomer, and it is more preferred if a portion is a monofunctional monomer and the other portion is a polyfunctional monomer. That is, the monomer component may contain two or more monomers (B), and it is more preferred that a portion of the two or more monomers (B) is a monofunctional monomer and the other portion is a polyfunctional monomer.

Among the monomers (B), the monofunctional monomers include, for example, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate (2-HPA), 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropylphthalic acid, EO-modified phenol (meth)acrylate, EO-modified cresol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, PO-modified nonylphenol (meth)acrylate, The invention also includes the following: 1, 2-diphenylphenol (meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, benzyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and the like.

Among the monomers (B), those belonging to the multifunctional monomers include, for example, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ethoxylated trihydroxymethylpropane tri(meth)acrylate, propoxylated trihydroxymethylpropane tri(meth)acrylate. , pentaerythritol tri(meth)acrylate, dihydroxymethylpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, etc.

The photopolymerization initiator may be any compound that can be activated by active light such as visible light or ultraviolet light and initiates or promotes the polymerization of the monomer components. The photopolymerization initiator may be used alone or in combination of two or more. The photopolymerization initiator is preferably a photo-radical polymerization initiator.

The photo-free radical polymerization initiator can be enumerated as follows: benzophenone and its derivatives; benzoyl and its derivatives; anthraquinone and its derivatives; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoyl dimethyl ketal and other benzoin-type photopolymerization initiators; diethoxyacetophenone, 4-tert-butyltrichloroacetophenone and other acetophenone-type photopolymerization initiators; 2-dimethylaminobenzoic acid ethyl ester; p-dimethylaminobenzoic acid ethyl ester; diphenyl disulfide; 9-oxothiophenone and its derivatives; camphorquinone type photopolymerization initiators such as 7,7-dimethyl-2,3-dioxybiscyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxybiscyclo[2.2.1]heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxybiscyclo[2.2.1]heptane-1-carboxy-2-methyl ester, and 7,7-dimethyl-2,3-dioxybiscyclo[2.2.1]heptane-1-carboxyl chloride; α-aminoalkylphenyl ketone type photopolymerization initiators such as 2-methyl-1-[4-(methylthio)phenyl]-2-thiazol-1-one and 2-benzyl-2-dimethylamino-1-(4-thiazol-1-phenyl)-butanone-1; Acylphosphine oxide type photopolymerization initiators such as benzoyldiphenylphosphine oxide, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, benzoyldiethoxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Methyl phenylglyoxylate; Ethyl oxyphenylacetate-2-[2-oxo-2-phenyl-acetyloxy-ethoxy]-ethyl ester; Oxyphenylacetic acid-2-[2-hydroxy-ethoxy]-ethyl ester; etc.

As for the photopolymerization initiator, considering that it can be cured only with visible light above 390nm, an acylphosphine oxide type photopolymerization initiator is preferred. In addition, an acylphosphine oxide type photopolymerization initiator can also be referred to as a photopolymerization initiator having an acylphosphine oxide group (-(C=O)-(P=O)<). Moreover, considering that it can be cured with light above 395nm and that a cured body with a higher visible light transmittance can be easily obtained, diphenyl-2,4,6-trimethylbenzylphosphine oxide is particularly preferred. Examples of diphenyl-2,4,6-trimethylbenzylphosphine oxide include "Irgacure TPO" manufactured by BASF JAPAN.

The content of the photopolymerization initiator is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and even more preferably 2.5 parts by mass or more, relative to 100 parts by mass of the total amount of the monomer components. By increasing the content of the photopolymerization initiator, the curing performance of the composition tends to be further improved. The content of the photopolymerization initiator is preferably 12 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less, relative to 100 parts by mass of the total amount of the monomer components. By reducing the content of the photopolymerization initiator, it becomes easier to obtain a cured body with a higher visible light transmittance. That is, the content of the photopolymerization initiator, relative to 100 parts by mass of the total monomer component, can be, for example, 0.05-12 parts by mass, 0.05-8 parts by mass, 0.05-6 parts by mass, 0.5-12 parts by mass, 0.5-8 parts by mass, 0.5-6 parts by mass, 2-12 parts by mass, 2-8 parts by mass, 2-6 parts by mass, 2.5-12 parts by mass, 2.5-8 parts by mass or 2.5-6 parts by mass.

The composition of this embodiment may further include other components besides the monomer component and the photopolymerization initiator. The composition of this embodiment may further include, for example, known additives that can be used in the field of sealants for organic EL display elements. Examples of additives include antioxidants, metal passivating agents, fillers, stabilizers, neutralizers, lubricants, antibacterial agents, etc.

The composition of the present embodiment can be hardened by irradiating at least one of visible light or ultraviolet light. In addition, in this specification, the "hardening" of the composition is not limited to rigid solidification, as long as the monomer components are polymerized to form a polymer. For example, the hardened body of the composition can be a rigid solid (e.g., glass) or a rubbery body.

Energy sources for irradiating visible light or ultraviolet light include: deuterium lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, xenon-mercury mixed lamps, halogen lamps, excimer lamps, indium lamps, cobalt lamps, LED lamps, electrodeless discharge lamps and other energy sources.

The composition of this embodiment is preferably cured by light with a wavelength of 380 nm or more, preferably by light with a wavelength of 395 nm or more, and most preferably by light with a wavelength of 395 nm, from the viewpoint of not easily damaging the organic EL display element. The wavelength of the irradiation light is preferably 500 nm or less, from the viewpoint of avoiding the possibility of temperature rise of the irradiated part caused by infrared light and damaging the organic EL display element. The energy irradiation source is preferably an LED lamp with a single-wavelength luminescence wavelength.

The irradiation amount when hardening the composition is preferably 100 to 8000 mJ/cm ² , and more preferably 300 to 2000 mJ/cm ² . By controlling the irradiation amount to be above 100 mJ/cm ² , the composition can be sufficiently hardened and high bonding strength can be easily obtained. In addition, by controlling the irradiation amount to be below 8000 mJ/cm ² , the composition can be hardened without causing damage to the organic EL display element. That is, the irradiation amount when hardening the composition can be, for example: 100 to 8000 mJ/cm ² , 300 to 8000 mJ/cm ² , 100 to 2000 mJ/cm ² , 300 to 2000 mJ/cm ² .

The cured product of the composition of this embodiment preferably has excellent transparency. Specifically, the spectral transmittance of the cured product in the ultraviolet-visible light region of 360 nm or more and 800 nm or less is preferably 95% or more, more preferably 97% or more, and even more preferably 99% or more per 10 μm thickness. If the spectral transmittance is 95% or more, an organic EL display device with excellent brightness and contrast can be easily obtained.

The moisture permeability of the cured product of the composition of this embodiment measured at 100 μm thickness after exposure to 85°C and 85% RH for 24 hours is preferably 500 g/m ² or less, more preferably 400 g/m ² or less, and even more preferably 350 g/m ² or less. If the moisture permeability is low, the generation of black spots caused by moisture reaching the organic light-emitting material layer can be more significantly suppressed.

The method of using the composition of this embodiment is not particularly limited. The composition of this embodiment can be ideally used as a sealant for an organic EL display element. Specifically, for example, by applying the composition to an object (e.g., an organic EL display element) and curing the composition on the object, a sealant composed of a cured body of the composition can be formed.

Alternatively, the composition may be cured into a predetermined shape (e.g., a film shape, a sheet shape, etc.) to form a sealing material having a predetermined shape. In this case, for example, the sealing material may be placed on an organic EL display element to seal the organic EL display element.

Since the composition of this embodiment has excellent surface flatness and straightness, even when applied to the inkjet method, an organic film with few surface irregularities can be accurately formed within a predetermined range. Therefore, the composition of this embodiment can be ideally used as a coating liquid for forming an organic film (preferably an organic film used as a sealing material for an organic EL display element) using the inkjet method.

Hereinafter, an organic EL display device formed by using the composition of the present embodiment as a sealant will be described by taking a top emission type organic EL display device as an example. In addition, the organic EL display device to which the composition of the present embodiment is applied is not limited to the top emission type, and may also be a bottom emission type organic EL display device in which light generated by the organic EL layer is irradiated from the substrate side.

A top-emitting organic EL display device includes an organic EL display element, a sealing layer for sealing the organic EL display element, and a sealing substrate disposed on the sealing layer.

An organic EL display element has, for example, a structure in which an anode, an organic EL layer including a light-emitting layer, and a cathode are sequentially stacked on a substrate.

The substrate of the organic EL display element can be, for example, a glass substrate, a silicon substrate, a plastic substrate, etc. Among them, a glass substrate and a plastic substrate are preferred, and a glass substrate is more preferred.

The plastics used for the plastic substrate can be listed as: polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polybenzimidazole, polybenzobisthiazole, polybenzoxazole, polythiazole, polyphenylene styrene, polymethyl methacrylate, polystyrene, polycarbonate, polycycloolefin, polyacrylic acid, etc. Among them, from the viewpoint of low water permeability, low oxygen permeability and excellent heat resistance, it is preferably one or more of the group consisting of polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polybenzimidazole, polybenzobisthiazole, polybenzoxazole, polythiazole and polyphenylene glycol. From the viewpoint of high permeability of energy rays such as ultraviolet rays or visible rays, it is more preferably one or more of the group consisting of polyimide, polyetherimide, polyethylene terephthalate and polyethylene naphthalate.

Generally speaking, the anode uses a conductive metal oxide film or a semi-transparent metal film with a large work function (a work function greater than 4.0 eV is preferred). Examples of the material of the anode include metal oxides such as indium tin oxide (ITO) and tin oxide; metals such as gold (Au), platinum (Pt), silver (Ag), and copper (Cu), or alloys containing at least one of them; organic transparent conductive films such as polyaniline or its derivatives, polythiophene or its derivatives, etc. If necessary, the anode can be formed by two or more layers. The film thickness of the anode can be appropriately selected in consideration of conductivity (and in the case of bottom emission, also in consideration of light transmittance). The thickness of the anode is preferably 10nm to 10μm, more preferably 20nm to 1μm, and most preferably 50nm to 500nm. That is, the thickness of the anode can be, for example, 10nm to 10μm, 10nm to 1μm, 10nm to 500nm, 20nm to 10μm, 20nm to 1μm, 20nm to 500nm, 50nm to 10μm, 50nm to 1μm, or 50nm to 500nm. The anode can be made by vacuum evaporation, sputtering, ion plating, plating, etc. In the case of top emission, a reflective film can also be provided under the anode to reflect the light irradiated to the substrate side.

The organic EL layer at least includes a luminescent layer composed of organic matter. The luminescent layer contains luminescent materials. Examples of luminescent materials include organic substances (low molecular weight compounds or high molecular weight compounds) that emit fluorescence or phosphorescence. The luminescent layer may also contain doped materials. Examples of organic substances include pigment materials, metal complex materials, high molecular weight materials, etc. Doped materials are doped into organic substances in order to improve the luminescent efficiency of organic substances, change the luminescent wavelength, etc. The thickness of the luminescent layer composed of these organic substances and dopants doped as needed is usually 2 to 200 nm.

Pigment materials include: methylcyclopentamine derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanyl amine derivatives, oxadiazole dimers, pyrazoline dimers, etc.

Metal complex materials include: iridium complexes, platinum complexes, etc., which have luminescence from triplet excited states; quinolinol aluminum complexes, benzoquinolinol ceria complexes, benzoxazole zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, cerium complexes, etc. Metal complexes include: rare earth metals such as zirconium (Tb), cerium (Eu), and dysprosium (Dy) as the central metal; aluminum (Al), zinc (Zn), ceria (Be), etc., and metal complexes having diazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structures, etc. as the ligands. Among them, a metal complex having aluminum (Al) as a central metal and a quinoline structure or the like as a ligand is preferred. Among the metal complexes having aluminum (Al) as a central metal and a quinoline structure or the like as a ligand is preferred, tris(8-hydroxyquinoline)aluminum is preferred.

Examples of the polymer material include poly(p-phenylene vinylene) derivatives, polythiophene derivatives, poly(p-phenylene) derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and polymerized versions of the above-mentioned pigments or metal complex-based luminescent materials.

Among the above-mentioned luminescent materials, materials emitting blue light include: stilbene arylene derivatives, oxadiazole derivatives, polyvinyl carbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, and polymers thereof. Among them, polymer materials are preferably selected from the group consisting of polyvinyl carbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives.

Materials emitting green light include quinacridone derivatives, coumarin derivatives, poly(p-phenylene vinylene) derivatives, polyfluorene derivatives, and polymers thereof. Among them, polymer materials are preferred. Among polymer materials, one or more of the group consisting of poly(p-phenylene vinylene) derivatives and polyfluorene derivatives are preferred.

The materials emitting red light include coumarin derivatives, thiophene ring compounds, poly(p-phenylene vinylene) derivatives, poly(thiophene) derivatives, polyfluorene derivatives, and polymers thereof. Among them, polymer materials are preferred. Among polymer materials, one or more of the group consisting of poly(p-phenylene vinylene) derivatives, polythiophene derivatives, and polyfluorene derivatives are preferred.

The doping materials include: perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squarylium derivatives, porphyrin derivatives, styrene pigments, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, etc.

In addition to the light-emitting layer, the organic EL layer may also be appropriately provided with: a layer provided between the light-emitting layer and the anode, and a layer provided between the light-emitting layer and the cathode. First, the layer provided between the light-emitting layer and the anode may include: a hole injection layer for improving the injection efficiency of holes from the anode, a hole transport layer for transferring holes injected from the anode or the hole injection layer to the light-emitting layer, etc. The layer provided between the light-emitting layer and the cathode may include: an electron injection layer for improving the injection efficiency of electrons from the cathode, an electron transport layer for transferring electrons injected from the cathode or the electron injection layer to the light-emitting layer, etc.

Materials for forming the hole injection layer include: phenylamine series such as 4',4''-tris(2-naphthyl(phenyl)amino)triphenylamine; starburst amine series; phthalocyanine series; oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide; amorphous carbon, polyaniline, polythiophene derivatives, etc.

Materials constituting the hole transport layer include: polyvinyl carbazole or its derivatives, polysilane or its derivatives, polysiloxane derivatives having aromatic amines in the side chains or main chains, pyrazoline derivatives, aromatic amine derivatives, distilbene derivatives, triphenyldiamine derivatives, benzidine derivatives, polyaniline or its derivatives, polythiophene or its derivatives, polyarylamine or its derivatives, polypyrrole or its derivatives, poly(p-phenylene) or its derivatives, poly(2,5-thiopheneethylene) or its derivatives, etc.

When these hole injection layers or hole transport layers have the function of preventing the transport of electrons, they are sometimes also called electron blocking layers.

Materials constituting the electron transport layer include: oxadiazole derivatives, anthraquinone dimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyanoanthraquinone dimethane or its derivatives, fluorenone derivatives, diphenyl dicyanoethylene or its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyfluorene or its derivatives, etc. Derivatives include: metal complexes, etc. Among them, 8-hydroxyquinoline or its derivatives are preferred. Among 8-hydroxyquinoline or its derivatives, from the viewpoint that it can also be used as a fluorescent or phosphorescent organic substance contained in the light-emitting layer, tris(8-hydroxyquinoline)aluminum is preferred.

The electron injection layer may be a single layer structure of a calcium (Ca) layer, or a single layer structure of a layer formed of one or more metals of Group IA and Group IIA of the periodic table with a work function of 1.5 to 3.0 eV and oxides, halides and carbonates of the metals, or a stacked structure of a layer formed of one or more metals of Group IA and Group IIA of the periodic table with a work function of 1.5 to 3.0 eV and oxides, halides and carbonates of the metals, depending on the type of the light-emitting layer. Metals of Group IA of the Periodic Table of Elements with a work function of 1.5 to 3.0 eV or their oxides, halides, and carbonates include lithium (Li), lithium fluoride, sodium oxide, lithium oxide, lithium carbonate, etc. Metals of Group IIA of the Periodic Table of Elements with a work function of 1.5 to 3.0 eV or their oxides, halides, and carbonates include strontium (Sr), magnesium oxide, magnesium fluoride, strontium fluoride, barium fluoride, strontium oxide, magnesium carbonate, etc.

When these electron transport layers or electron injection layers have the function of preventing the transport of holes, they are sometimes also referred to as hole blocking layers.

The cathode should be a transparent or semi-transparent material with a small work function (preferably less than 4.0 eV) and easy to inject electrons into the light-emitting layer. The cathode materials include: lithium (Li), sodium (Na), potassium (K), chromium (Rb), cesium (Cs), benzene (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), aluminum (Al), stygium (Sc), vanadium (V), zinc (Zn), yttrium (Y), indium (In), thorium (Ce), samarium (Sm), eutectic (Eu), terbium (Tb), ytterbium (Yb) and other metals. ; or an alloy consisting of two or more of the above metals, or an alloy consisting of one or more of them and one or more of gold (Au), silver (Ag), platinum (Pt), copper (Cu), chromium (Cr), manganese (Mn), titanium (Ti), cobalt (Co), nickel (Ni), tungsten (W), tin (Sn); or graphite or graphite interlayer compound; or metal oxides such as ITO and tin oxide, etc.

The cathode may also be arranged in a stacked structure of more than two layers. Examples of stacked structures of more than two layers include: stacked structures of the above-mentioned metals, metal oxides, fluorides, alloys thereof, and metals such as Al, Ag, and Cr. The film thickness of the cathode may be appropriately selected in consideration of conductivity and durability. The film thickness of the cathode is preferably 10nm to 10μm, more preferably 15nm to 1μm, and most preferably 20nm to 500nm. That is, the film thickness of the cathode may be, for example: 10nm to 10μm, 10nm to 1μm, 10nm to 500nm, 15nm to 10μm, 15nm to 1μm, 15nm to 500nm, 20nm to 10μm, 20nm to 1μm, or 20nm to 500nm. The cathode production methods include: vacuum evaporation, sputtering, lamination of metal thin films by heat pressing, etc.

These layers provided between the light-emitting layer and the anode, and between the light-emitting layer and the cathode, can be appropriately selected according to the performance required of the organic EL display device to be manufactured. For example, the structure of the organic EL display element used in this embodiment can have any of the following layer structures (i) to (xv). (i) Anode/hole transport layer/luminescent layer/cathode (ii) Anode/luminescent layer/electron transport layer/cathode (iii) Anode/hole transport layer/luminescent layer/electron transport layer/cathode (iv) Anode/hole injection layer/luminescent layer/cathode (v) Anode/luminescent layer/electron injection layer/cathode (v i) Anode/hole injection layer/luminescent layer/electron injection layer/cathode (vii) Anode/hole injection layer/hole transport layer/luminescent layer/cathode (viii) Anode/hole transport layer/luminescent layer/electron injection layer/cathode (ix) Anode/hole injection layer/hole transport layer/luminescent layer/electron injection layer/ Cathode (x) Anode/hole injection layer/luminescent layer/electron transport layer/cathode (xi) Anode/luminescent layer/electron transport layer/electron injection layer/cathode (xii) Anode/hole injection layer/luminescent layer/electron transport layer/electron injection layer/cathode (xiii) Anode/hole injection layer/hole transport layer /luminescent layer/electron transport layer/cathode (xiv)Anode/hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode (xv)Anode/hole injection layer/hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode (Here, "/" indicates that the layers are stacked adjacent to each other. The same applies to the following.)

The sealing layer is used to prevent water vapor, oxygen and other gases from contacting the organic EL display element, and is provided by sealing the organic EL display element with a layer having a high barrier to the above gases. The sealing layer is formed by alternating inorganic films and organic films from the bottom. The inorganic/organic laminate can also be formed by repeating it more than twice.

The inorganic film of the inorganic/organic laminate is a film provided to prevent the organic EL display element from being exposed to gases such as water vapor and oxygen in the environment where the organic EL display device is placed. The inorganic film of the inorganic/organic laminate is preferably a continuous and dense film with few defects such as pinholes. Examples of the inorganic film include single films such _as SiN film, SiO film, SiON film, _Al2O3 film, AlN film, or laminated films thereof.

The organic film of the inorganic/organic laminate is provided to cover defects such as pinholes formed on the inorganic film and to give flatness to the surface. The organic film is formed in a narrower area than the area formed by the inorganic film. This is because if the organic film is formed to be the same as or wider than the area formed by the inorganic film, the area where the organic film is exposed will deteriorate. However, the uppermost organic film formed on the uppermost layer of the entire sealing layer is formed in an area roughly the same as the area formed by the inorganic film. Moreover, the top surface of the sealing layer is formed in a flattened manner. The organic film can be a film formed using the composition of the above-mentioned embodiment (i.e., a film containing a hardened body of the composition).

As described above, the composition of this embodiment is suitable for inkjet coating, and the inkjet coating has excellent sprayability and flatness after inkjet coating. If the inkjet coating method is used, an organic film can be formed at a high speed and uniformly.

If the sealing layer is counted as one group of inorganic/organic stacking bodies, it is preferable to have 1 to 5 groups. This is because when there are 6 or more groups of inorganic/organic stacking bodies, the sealing effect on the organic EL display element is roughly the same as that of 5 groups. The thickness of the inorganic film of the inorganic/organic stacking body is preferably 50nm to 1μm. The thickness of the organic film of the inorganic/organic stacking body is preferably 1 to 15μm, and more preferably 3 to 10μm. If the thickness of the organic film is 1μm or more, it can completely cover the particles generated when the element is formed, and can be applied to the inorganic film with good flatness. If the thickness of the organic film is less than 15μm, moisture will not penetrate from the side of the organic film, and the reliability of the organic EL display element will be improved. The thickness of the organic film of the inorganic/organic laminate may be, for example, 1-15 μm, 1-10 μm, 3-15 μm, or 3-10 μm.

The sealing substrate is formed by covering the entire top surface of the uppermost organic film of the sealing layer. The sealing substrate can be the aforementioned substrate. Among them, it is preferably a substrate that is transparent to visible light. Among the substrates that are transparent to visible light (transparent sealing substrates), it is preferably one or more of the group consisting of a glass substrate and a plastic substrate, and a glass substrate is more preferred.

The thickness of the transparent sealing substrate is preferably 1 μm to 1 mm, more preferably 10 μm to 800 μm, and most preferably 50 μm to 300 μm. By placing the transparent sealing substrate above the sealing layer, the degradation of the surface of the uppermost organic film when it contacts the gas can be suppressed, and the barrier property of the organic EL display device can be improved. The thickness of the transparent sealing substrate can be, for example, 1 μm to 1 mm, 1 μm to 800 μm, 1 μm to 300 μm, 10 μm to 1 mm, 10 μm to 800 μm, 10 μm to 300 μm, 50 μm to 1 mm, 50 μm to 800 μm, or 50 μm to 300 μm.

Next, a method for manufacturing an organic EL display device having such a structure is described. First, an anode patterned into a predetermined shape, an organic EL layer including a light-emitting layer, and a cathode are sequentially formed on a first substrate by a known method to form an organic EL display element. For example, when the organic EL display device is used as a dot matrix display device, a bank is formed to divide the light-emitting area into a matrix shape, and the organic EL layer including the light-emitting layer is formed in the area surrounded by the bank.

Then, on the substrate formed with the organic EL display element, a first inorganic film having a predetermined thickness is formed by a film forming method such as a PVD (Physical Vapor Deposition) method such as a sputtering method, or a CVD method such as a plasma CVD (Chemical Vapor Deposition) method. Thereafter, the composition (sealant) of the present embodiment is attached to the first inorganic film by a film forming method such as a solution coating method, a spray coating method, or a flash coating method, an inkjet method, or the like. Among them, the inkjet method is preferred from the perspective of productivity. Thereafter, by irradiating energy rays such as ultraviolet rays and visible rays, the sealant is hardened and the first organic film is formed. A set of inorganic/organic laminates is formed by the above steps. The curing rate of the sealant is not particularly limited as long as the effect of the present embodiment can be exerted. For example, it can be set to 90% or more, preferably 95% or more, based on the value obtained by the measurement method described below.

The steps of forming the inorganic/organic stack as shown above are repeated a predetermined number of times. However, for the last set, i.e., the top inorganic/organic stack, the top surface can be flattened by applying a sealant to the top surface of the inorganic film by a coating method, flash coating method, inkjet method, etc.

Then, a transparent sealing substrate is bonded to the surface of the substrate to which the sealant is attached. Position alignment is performed during bonding. Thereafter, the sealant of this embodiment that is present between the upper inorganic film and the transparent sealing substrate is hardened by irradiating energy rays from the transparent sealing substrate side. In this way, the sealant is hardened and the uppermost organic film is formed, and at the same time, the uppermost organic film and the transparent sealing substrate are bonded. As described above, the manufacturing method of the organic EL display device is completed.

After the sealant is attached to the inorganic film, it may be partially irradiated with energy rays to polymerize it. By doing so, the shape of the uppermost organic film can be prevented from collapsing when the transparent sealing substrate is supported. The thickness of the inorganic film and the organic film may be the same for each inorganic/organic laminate or different for each inorganic/organic laminate.

In this embodiment, the organic EL display device can be used as a planar light source, a segment display device, or a dot matrix display device.

The above has been described with respect to the ideal implementation form of the present invention, but the present invention is not limited to the above implementation form. [Implementation Example]

The present invention is described in more detail below using embodiments, but the present invention is not limited to the embodiments.

The details of the components used in the examples and comparative examples are as follows. In addition, the viscosity of the monomer component is the value measured at 25°C using an E-type viscometer. ＜Fluorine-containing monomer＞ ･"13F" Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat 13F" Compound name: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate Viscosity: 4mPa･s ･"LINC-162A" Kyoeisha Chemical Co., Ltd., trade name "LINC-162A" Compound name: 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexafluoro-1,10-decane diacrylate Viscosity: 32mPa･s

<Monomer (B)> ･"A-LEN-10" Made by Shin-Nakamura Chemical Industry Co., Ltd., trade name "NK ESTER A-LEN-10" Compound name: Ethoxylated o-phenylphenol acrylate Viscosity: 150mPa･s ･"DCPA" Made by Shin-Nakamura Chemical Industry Co., Ltd., trade name "NK ESTER A-DCP" Compound name: Tricyclodecanedimethanol diacrylate Viscosity: 120mPa･s ･"BPE200" Made by Shin-Nakamura Chemical Industry Co., Ltd., trade name "NK ESTER BPE-200" Compound name: Ethoxylated bisphenol A dimethacrylate Viscosity: 600mPa･s ･"SR262" Made by ARKEMA, trade name "SR262" Compound name: 1,12-dodecanediol dimethacrylate Viscosity: 12mPa･s

<Photopolymerization initiator> ･"TPO" Made by iGM Resins, trade name "Omnirad TPO" Compound name: Diphenyl-2,4,6-trimethylbenzylphosphine oxide

(Example 1) 1 mass part of "LINC-162A", 5 mass parts of "A-LEN-10", 5 mass parts of "DCPA", 89 mass parts of "SR262", and 3.5 mass parts of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorine-containing monomer was set to 1 mass%, the ratio of the high-viscosity monomer was set to 10 mass%, and the ratio of the difunctional monomer was set to 95 mass%. The viscosity of the obtained composition (measured by an E-type viscometer at 25°C) was 13 mPa･s.

(Example 2) 1 mass part of "LINC-162A", 5 mass parts of "A-LEN-10", 18 mass parts of "DCPA", 76 mass parts of "SR262", and 3.5 mass parts of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorine-containing monomer was set to 1 mass%, the ratio of the high-viscosity monomer was set to 23 mass%, and the ratio of the difunctional monomer was set to 95 mass%. The viscosity of the obtained composition (measured by an E-type viscometer at 25°C) was 16 mPa･s.

(Example 3) 1 mass part of "LINC-162A", 5 mass parts of "A-LEN-10", 50 mass parts of "DCPA", 44 mass parts of "SR262", and 3.5 mass parts of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorine-containing monomer was set to 1 mass%, the ratio of the high-viscosity monomer was set to 55 mass%, and the ratio of the difunctional monomer was set to 95 mass%. The viscosity of the obtained composition (measured by an E-type viscometer at 25°C) was 36 mPa･s.

(Example 4) 0.01 mass parts of "LINC-162A", 5 mass parts of "A-LEN-10", 18 mass parts of "DCPA", 76.99 mass parts of "SR262", and 3.5 mass parts of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorine-containing monomer was set to 0.01 mass%, the ratio of the high-viscosity monomer was set to 23 mass%, and the ratio of the difunctional monomer was set to 95 mass%. The viscosity of the obtained composition (measured by an E-type viscometer at 25°C) was 16 mPa･s.

(Example 5) 90 parts by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 5 parts by mass of "DCPA", and 3.5 parts by mass of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorine-containing monomer was set to 90% by mass, the ratio of the high-viscosity monomer was set to 10% by mass, and the ratio of the difunctional monomer was set to 95% by mass. The viscosity of the obtained composition (measured at 25°C using an E-type viscometer) was 35 mPa･s.

(Example 6) 1 mass part of "LINC-162A", 5 mass parts of "A-LEN-10", 15 mass parts of "DCPA", 3 mass parts of "BPE200", 76 mass parts of "SR262", and 3.5 mass parts of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorine-containing monomer was set to 1 mass%, the ratio of the high-viscosity monomer was set to 23 mass%, and the ratio of the difunctional monomer was set to 95 mass%. The viscosity of the obtained composition (measured by an E-type viscometer at 25°C) was 17 mPa･s.

(Example 7) 1 part by mass of "13F", 5 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 76 parts by mass of "SR262", and 3.5 parts by mass of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorine-containing monomer was set to 1% by mass, the ratio of the high-viscosity monomer was set to 23% by mass, and the ratio of the difunctional monomer was set to 94% by mass. The viscosity of the obtained composition (measured at 25°C using an E-type viscometer) was 16 mPa･s.

(Comparative Example 1) 1 mass part of "LINC-162A", 99 mass parts of "SR262", and 3.5 mass parts of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorine-containing monomer was set to 1 mass%, the ratio of the high-viscosity monomer was set to 0 mass%, and the ratio of the difunctional monomer was set to 100 mass%. The viscosity of the obtained composition (measured by an E-type viscometer at 25°C) was 12 mPa･s.

(Comparative Example 2) 1 mass part of "LINC-162A", 5 mass parts of "A-LEN-10", 94 mass parts of "DCPA", and 3.5 mass parts of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorine-containing monomer was set to 1 mass%, the ratio of the high-viscosity monomer was set to 99 mass%, and the ratio of the difunctional monomer was set to 95 mass%. The viscosity of the obtained composition (measured by an E-type viscometer at 25°C) was 120 mPa･s.

(Comparative Example 3) 5 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 77 parts by mass of "SR262", and 3.5 parts by mass of "TPO" were mixed to prepare a composition. That is, among the monomer components, the ratio of the fluorinated monomer was set to 0% by mass, the ratio of the high viscosity monomer was set to 23% by mass, and the ratio of the difunctional monomer was set to 95% by mass. The viscosity of the obtained composition (measured by an E-type viscometer at 25°C) was 16 mPa･s.

The compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated by the following method. The results are shown in Tables 1 and 2.

<E-type viscosity> The viscosity of the composition was measured using an E-type viscometer (cone plate type: cone angle 1°34′, cone rotor radius 24 mm) at a temperature of 25°C and a rotation speed of 100 rpm. <Surface tension> The surface tension of the composition was measured using a contact angle meter (DM500 manufactured by Kyowa Interface Sciences) at 23°C using the pendant drop method.

<Evaluation of surface flatness> On a 70mm×70mm×0.7mmt substrate (alkaline-free glass (Eagle XG manufactured by Corning)), grooves of 25μm×25μm×3μmt were made at intervals of 10μm in the front, back, left and right directions by etching. Then, a 200nm SiN film was formed on the substrate with the grooves by plasma CVD. Then, an inkjet spraying device (MID500B manufactured by Musashi Engineering Co., Ltd., solvent-based spray head "MID HEAD") was used to pattern the composition in a manner of 15mm×15mm×8μmt. In addition, before pattern coating, the substrate was cleaned with acetone and isopropyl alcohol, respectively, and then cleaned for 5 minutes using a UV ozone cleaning device UV-208 manufactured by Technovision. After the pattern was applied, it was placed in a nitrogen environment at a temperature of 23°C and a relative humidity of 50% for ⁴ minutes. In the nitrogen environment, the composition was photocured using an LED lamp (UV-LED LIGHT SOURCE H-4MLH200-V1 manufactured by HOYA) emitting light at a wavelength of 395nm, with the cumulative light quantity of the light at a wavelength of 395nm reaching 1,500mJ/cm2. Then, the thickness of the cured film was measured in a direction perpendicular to the direction of movement of the printhead using a stylus-type shape measuring device (DektakXT manufactured by BRUKER). The difference between the maximum and minimum thicknesses in the plane after excluding 0.2mm from the end of the cured film was used as the evaluation result of the surface flatness.

<Evaluation of linearity> A 200 nm SiN film was formed by plasma CVD on a 70 mm × 70 mm × 0.7 mm substrate (alkaline-free glass (Eagle XG manufactured by Corning)). Then, the composition was patterned on a predetermined area to form a 15 mm × 15 mm × 8 μmt using an inkjet spraying device (MID500B manufactured by Musashi Engineering Co., Ltd., solvent-based spray head "MID HEAD"). After the pattern was applied, it was placed in a nitrogen environment for 4 minutes at a temperature of 23°C and a relative humidity of 50%. In the nitrogen environment, the composition was photocured using an LED lamp (HOYA UV-LED LIGHT SOURCE H-4MLH200-V1) emitting light at a wavelength of 395nm, with the cumulative light intensity of the light at a wavelength of 395nm reaching 1,500mJ/ ^cm2 . The length of the area of the cured body that exceeded the specified value was then measured using an optical microscope, with 15 locations per side, for a total of 60 locations, and the maximum value was taken as the linearity value.

<Evaluation of moisture permeability> A sheet-shaped hardened body with a thickness of 0.1 mm was prepared using the above-mentioned light curing conditions. According to JIS Z0208:1976 "Test method for moisture permeability of moisture-proof packaging materials (cup method)", calcium chloride (anhydrous) was used as a moisture absorbent, and the moisture permeability of the hardened body with a thickness of 100 μm was measured at a temperature of 85°C and a relative humidity of 85% for 24 hours.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Surface flatness (nm) 140 110 380 300 45 80 115 Straightness(μm) 195 140 50 135 240 100 150 Moisture permeability (g/m ² ) 295 260 220 260 200 265 275

[Table 2] Comparison Example 1 Comparison Example 2 Comparison Example 3 Surface flatness (nm) 100 - 500 Straightness(μm) 450 - 145 Moisture permeability (g/m ² ) 305 210 260

As shown in Table 1, the composition of the embodiment can achieve both excellent surface flatness and straightness. In addition, the moisture permeability of the hardened body formed by the composition of the embodiment is sufficiently low, and it is confirmed that it is effective as a sealing material for an organic EL display element.

As shown in Table 2, the coating liquid of Comparative Example 1 tends to meander during inkjet coating, resulting in poor straightness. Comparative Example 3 also results in poor surface flatness. In addition, the composition of Comparative Example 2 has a high viscosity and is difficult to spray from the inkjet nozzle, so the surface flatness and straightness cannot be evaluated.

Claims (10)

A composition comprising: a monomer component, which is composed of a fluorine-containing monomer having a fluorine atom and a (meth)acryl group, and a monomer (B) having a (meth)acryl group and no fluorine atom, and a photopolymerization initiator; 5-23% by mass of the monomer component is a high viscosity monomer having a viscosity of 50 mPa.s or more measured at 25°C using an E-type viscometer, the viscosity of the composition measured at 25°C using an E-type viscometer is 3 mPa.s or more and 50 mPa.s or less, and 0.1-10% by mass of the monomer component is the fluorine-containing monomer. As in claim 1, the composition, wherein at least a portion of the monomer components is a multifunctional monomer having more than two carbon-carbon unsaturated double bonds. As in claim 2, the composition, wherein 70-98% by mass of the monomer component is the multifunctional monomer. As claimed in claim 1, at least a portion of the high viscosity monomer is a monofunctional monomer having one carbon-carbon unsaturated double bond. As in the composition of claim 4, wherein 10-60 mass % of the high viscosity monomer is the monofunctional monomer. If the composition of any one of claim 1 to 5 is a sealant for an organic electroluminescent display element. A hardened body obtained by hardening a composition as described in any one of claims 1 to 6. A sealing material for an organic electroluminescent display element, comprising a hardened body as described in claim 7. A sealing material for an organic electroluminescent display element, comprising a laminate formed by laminating an inorganic film and an organic film, wherein the organic film comprises a hardened body as described in claim 7. An organic electroluminescent display device, comprising: an organic electroluminescent display element, and a sealing material for the organic electroluminescent display element as claimed in claim 8 or 9.